Triazole-Decorated Porphyrin Cathodes Enabling Reversible Chloroaluminate Storage for High-PerformanceAluminum-Ion Batteries

The emergence of rechargeable aluminum-ion batteries (AIBs) as potential successors in the field of energy storage is predicated on the substantial theoretical capacity, natural availability, cost-effectiveness, and intrinsic stability of metallic aluminum. Nevertheless, the intense electrostatic forces between multivalent aluminum ions and their host structures frequently result in retarded reaction rates and compromised cycling durability, presenting impediments to the engineering of superior AIBs cathodes. Herein, we report 5,10,15,20-tetrakis[4-(1,2,4-triazol-1-yl)phenyl]porphyrin (H2TTPP), a triazole-functionalized porphyrin, as an efficient organic cathode for AIBs. The constructed H2TTPP-based AIBs exhibit a substantial operational potential of 1.495 V and a primary charging capacity of 202.2 mAh g–1 at a current density of 40 mA g–1, while demonstrating superior rate performance up to 1000 mA g–1 and exceptional cyclability surpassing 10,000 cycles at 500 mA g–1. Further, at 80 mA g–1, the H2TTPP cathode's thermal performance was assessed between 40 and 70 °C, with the high capacity increasing to 216.3 mAh g–1 at 70 °C, while maintaining over 80% Coulombic efficiency (CE). Combined UV–vis spectroscopy, N K-edge X-ray absorption spectroscopy, and ex situ X-ray photoelectron spectroscopy demonstrate that reversible interactions between N active sites and chloroaluminate ions govern the charge-storage process. In addition, cable-type AIBs maintain stable electrochemical performance under mechanical bending.